The present invention relates to new water-dispersible or water-soluble sulphonated polyesters, to a process for their preparation and to their use as antisoiling and/or antiredeposition agent and optionally detergent in detergent compositions, in rinsing, softening or antisoiling (xe2x80x9cfinishingxe2x80x9d) treatment compositions, for washing with or without pretreatment, rinsing, softening or the antisoiling treatment of textiles, especially those polyester-based.
According to the invention these are water-dispersible or water-soluble sulphonated polyesters characterized in that they are capable of being obtained by esterification and/or transesterification and polycondensation of a monomer composition based:
on an unsulphonated diacidic monomer (A) consisting of at least one dicarboxylic acid or anhydride chosen from terephthalic, isophthalic and 2,6-naphthaleiedicarboxylic acids or anhydrides or their diesters, in a quantity corresponding to a molar ratio (A)/(A)+(SA) of the order of 9S/100 to 60/100, preferably of the order of 93/100 to 65/100
on a sulphonated diacidic monomer (SA) consisting of at least one sulphonated aromatic or sulphonated aliphatic dicarboxylic acid or anhydride, or their diesters, in a quantity corresponding to a molar ratio (SA)/(A)+(SA) of the order of 5/100 to 40/100, preferably of the order of 7/100 to 35/100, it being possible for up to 50 mol %, preferably up to 30 mol %, of the quantity of usulphonated diacidic monomer (A) and/or of sulphonated diacidic monomer (SA) to be replaced with a hydroxylated diacidic monomer (HA) consisting of at least one hydroxylated aromatic or aliphatic dicarboxylic acid or anhydride or a diester of the 8aid hydroxylated aromatic or aliphatic dicarboxylic acid
and on a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol, in a quantity corresponding to a ratio of number of OH functional groups of the polyol monomer (P)/number of COOS functional groups or functional group equivalents of the diacidic monomer (A)+(SA)+(HA) of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
in that the sulphonated diacidic monomer (SA) consists of at least one sulphonated aromatic dicarboxylic acid or anhydride or of a mixture of sulphonated aromatic acids or anhydrides and of sulphonated aliphatic acids or anhydrides or their diester when the polyol monomer (P) does not contain any polyol other than a glycol or when the hydroxylated diacidic monomer (HA) is absent and in that the said sulphonated polyesters exhibit
a number molecular mass lower than 20 000,
a sulphur weight content of the order of 0.5 to 10%, preferably of the order of 1.2 to 8%
and a hydroxyl functional group content, expressed as OH equivalent/kg of polymer, higher than 0.2.
The hydroxyl functional group contents are estimated by proton NMR; the measurement is carried out in dimethyl sulphoxide.
The number molecular manses are measured by gel permeation chromatography in dimethylacetamide containing 102 N of LiBr, at 25xc2x0 C. The results are expressed as polystyrene equivalents.
The elementary unit considered in the definition of the mole of monomer (A), (SA) or (HA) is the COOE functional group in the case of the diacids or the COOH functional group equivalent in the case of the anhydrides or of the diesters.
The unsulphonated diacidic monomer (A) preferably consists of 50 to 100 mol %, very particularly of 70 to 90 mol %, of terephthalic acid or anhydride or of one of its lower (methyl, ethyl, propyl, isopropyl, butyl) diesters and of 0 to 50 mol %, very particularly from 10 to 30 mol %, of isophthalic acid or anhydride and/or of 2,6-naphthalenedicarboxylic acid or anhydride or of one of their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters; the preferred diesters are methyl diesters.
In the unsulphonated diacidic monomer (A) there may additionally be present minor quantities of aromatic diacids other than those mentioned above, such as ortho-phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and biphenyl dicarboxylic acids or aliphatic diacids such as adipic, glutaric, succinic, triaethyladipic, pimelic, azelaic, sebacic, sueric, itaconic and maleic acids, etc. in the form of acid, anhydride or lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.
The sulphonated diacidic monomer (SA) has at least one sulphonic acid group, preferably in the form of an alkali metal (preferably sodium) sulphonate, and two acidic functional groups or acidic functional group equivalents (that is to nay an anhydride functional group or two ester functional groups) attached to one or a number of aromatic rings, when aromatic dicarboxylic acids or anhydrides or their diesters are involved, or to the aliphatic chain when aliphatic dicarboxylic acids or anhydrides or their diesters are involved.
Among the sulphonated diacidic monomers (SA), there may be mentioned aromatic sulphonated dicarboxylic acids or anhydrides such as sulphoisophthalic, sulphoterephthalic, sulpho-ortho-phthalic acids or anhydrides, 4-sulpho-2,7-naphthalenedicarboxylic acids or anhydrides, sulpho-4,4xe2x80x2-bis(hydroxycarbonyl)diphenyl sulphones, sulphodiphenyldicarboxylic acids or anhydrides, sulpho-4,4xe2x80x2-bis(hydroxycarbonyl)diphenylmethanes, sulpho-5-phenoxyisophthalic acids or anhydrides or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters and sulphonated aliphatic sulphonated dicarboxylic acids or anhydrides such an sulphosuccinic acids or anhydrides or their lower (methyl, ethyl, propyl, isopropyl, butyl) diester. The preferred sulphonated diacidic monomers (SA) are sulphoisophthalic and sulphosuccinic acids or anhydrides.and their methyl diesters and very particularly dimethyl 5-sodiooxysulphonylisophthalate.
The hydroxylated diacidic monomer (HA) has at least one hydroxyl group attached to one or a number of aromatic rings when it is an aromatic monomer or to the aliphatic chain when it is an aliphatic monomer.
Among the hydroxylated diacidic monomers (HA) there may be mentioned 5-hydroxyisophthalic, 4-hydroxyisophthalic, 4-hydroxyphthalic, 2-hydroxymethylsuccinic, hydroxymetbylglutaric and hydroxyglutaric acids or anhydrides etc., or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.
The polyol monomer (P) preferably used is monoethylene glycol and/or glycerol.
The said water-soluble and/or water-dispersible sulphonated polyesters can be obtained by the usual esterification and/or transesterification and polycondeneation processes, for example by an esterification and/or transesterification reaction, in the presence of a catalyst of esterification/transesterification of the polyol monomer (P) with the various diacidic monomers, each diacid being in the acid or anhydride form or in the form of one of its diesters, and polycondensation of the polyol eaters at reduced pressure in the presence of a polycondensation catalyst.
According to a preferred method of preparation the said water-soluble and/or water-dispersible sulphonated polyesters are obtained by carrying out the following successive stages:
a stage of transesterification (interchange) between, an the one hand, the sulphonated diacidic monomer (SA) in diester form and from 50 to 100 mol %, very particularly from 30 to 90 mol %, of the total quantity of the unsulphonated diacidic monomer (A), in diester form, and, on the other hand, a quantity of polyol monomer (P) corresponding to a ratio of number of OH functional groups, of the polyol monomer (P)/number of COOK functional group equivalents of the said monomers (A) and (SA) in the form of diesters of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3.0
an optional stage of esterification between the possible remaining quantity of the unsulphonated diacidic monomer (A), in diacid or anhydride form, and a quantity of polyol monomer (P) corresponding to a ratio of number of 09 functional groups of the polyol monomer (P)/number of COOH functional groups of the unsulphonated diacidic monomer (A) in diacid or anhydride form of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3.0
a polycondensation stage.
The diesters of the unsulphonated (A) and sulphonated (SA) dicarboxylic acids used in the transesterification (interchange) stage are preferably methyl diesters.
The interchange stage in performed at a temperature higher than or equal to 130xc2x0 C., preferably of the order of 140 to 220xc2x0 C. and very particularly of the order of 180 to 220xc2x0 C.; at this temperature the methanol formed (in the preferred case of the methyl diesters) is removed from the reaction mixture preferably by distillation. This interchange operation is preferably carried out in the presence of a metallic transesterification catalyst, especially a metal carboxylate such an manganese acetate, zinc acetate, cobalt acetate or calcium acetate, or of an organic or inorganic titanate such as butyl titanate, 2,2xe2x80x22xe2x80x3-nitrilotriethyl titanate (or titanium aminotriethanolate) or calcium titanate. The preferred catalysts are organic titanates; they are used in quantities of the order of at least 0.001% by weight, expressed as titanium, preferably of the order of 0.002% to 0.02% by weight of titanium relative to the weight of reactants present.
The duration of the interchange operation is from 1 to 4 hours; it is generally of the order of 2 to 3 hours.
When more than 90% of the theoretical quantity of methanol has been distilled the excess polyol is removed by raising the temperature of the reaction mixture to 230xc2x0 C.
The esterification operation is carried out by adding to the reaction mixture the remaining fraction of the unsulphonated diacidic monomer (A), in diacid form, and of the polyol monomer (P) suspended beforehand, at a temperature corresponding to that of the end of the interchange temperature; the addition period is of the order of 1 hour.
This esterification operation is carried out at a temperature of the order of 230 to 280xc2x0 C., preferably of the order of 250 to 260xc2x0 C., in the presence of a catalyst of the same type as that for transesterification; the preferred catalysts are organic titanates; they are used in quantities of the order of at least 0.001% by weight expressed as titanium, preferably of the order of 0.002% to 0.02% by weight of titanium relative to the weight of reactants introduced at the esterification stage; the reaction takes place with removal of water, which is drawn off from the reactor at the same time an the excess polyol,
The polycondensation operation is preferably carried out at a temperature of the order of 230 to 280xc2x0 C., preferably of,the order of 240 to 260xc2x0 C., in another reactor preheated to this temperature and gradually evacuated to a pressure which may be up to 10 Pa; a pressure reduction to approximately 10 millibars lasts of the order of 40 minutes.
The polycondensation operation takes place with removal of polyol molecules. This operation in stopped when the drive torque of the stirrer shaft shows a value equivalent to approximately 0.5 to 5 newton meters for a reaction mane temperature of 250xc2x0 C. and a stirring rate of 80 revolutions/minute of an anchor-shaped rotor in a 7.5-liter reactor; the torquemeter employed is of Kyowa type, the measurement range of which is between 0 and 100 newton meters.
The vacuum in next broken with nitrogen and the polymer is poured into an ingot mould; after cooling, the polymer in ground.
The preferred sulphonated polyesters are capable of being obtained from
terephthalic acid (A1) in (preferably methyl) diester form and isophthalic acid (A2) in the form of diacid or anhydride, or terephthalic acid (A1) in (preferably methyl) diester form and a hydroxylated terephthalic or hydroxylated isophthalic acid (HA) in the form of diacid or anhydride, optionally mixed with isophthalic acid (A2) it the form of diacid or anhydride, in an (A1)/(A1)+(A2), (A1)/(A1)+(HA) or (A1)/(A1)+(HA)+(A2) molar ratio of the order of 100/100 to 50/100, preferably of the order of 90/100 to 70/100 [as monomer (A) or monomers (A) and (HA)]
sulphoisophthalic acid in (preferably methyl) diester form [as monomer (SA)]
monoethylene glycol and/or glycerol [as polyol monomer (P)].
They may be prepared according to the preferred process described above, by carrying out the following successive stages:
a stage of transesterification (interchange) between, on the one hand, the (preferably methyl) diester of terephthalic acid (A1) and the (preferably methyl) diester of sulphoisophthalic acid (SA) and, on the other hand, monoethylene glycol and/or glycerol (P), the ratio of number of OH functional groups of (P)/number of COOH functional group equivalents of (A1)+(SA) being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5, and very 20 particularly of the order of 1.8 to 3
a stage of esterification between isophthalic acid (A2) and/or hydroxy(iso- or tere)phthalic acid (HA) and, on the other hand, monoethylens glycol and/or glycerol (P), the ratio of number of OH functional groups of (P)/number of COOE functional groups of (A2) +/or (HA) being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
a polycondensation stage.
The sulphonated polyesters forming the subject of the invention are very particularly advantageous as antisoiling and/or antiredeposition agents and optionally detergents in detergent compositions, in rinsing, softening or antisoiling (xe2x80x9cfinishingxe2x80x9d) treatment compositions for washing with or without pretreatment, rinsing, softening or antisoiling treatment of textiles, especially polyester-based.
A further subject of the present invention is detergent compositions containing of the order of 0.01 to 10%, preferably of the order of 0.1% to 5% and very particularly of the order of 0.2 to 3%, relative to the weight of the said compositions, of the said sulphonated polyesters forming the subject of the invention.
Another subject of the invention consists of the use, as antisoiling agents in detergent compositions for washing textile articles based especially on polyester fibres, of water-dispersible or water-soluble sulphonated polyesters capable of being obtained by esterification and/or transesterification and polycondensation of a monomer composition based:
on an unsulphonated diacidic monomer (A) consisting of at least one dicarboxylic acid or anhydride chosen from terephthalic, isophthalic and 2,6-naphthalenedicarboxylic acids or anhydrides or their diesters, in a quantity corresponding to a molar ratio (A)/(An+(SA) of the order of 95/100 to 60/100, preferably of the order of 93/100 to 65/100
on a sulphonated diacidic monomer (SA) consisting of at least one sulphonated aromatic or sulphonated aliphatic dicarboxylic acid or anhydride, or their diesters, in a quantity corresponding to a molar ratio (SA)/(A)+(SA) of the order of 5/100 to 40/100, preferably of the order of 7/100 to 35/100, it being possible for up to 50 mol %, preferably up to 30 mol %, of the quantity of unsulphonated diacidic monomer (A) and/or of sulphonated diacidic monomer (SA) to be replaced with a hydroxylated diacidic monomer (HA) consisting of at least one hydroxylated aromatic or aliphatic dicarboxylic acid or anhydride or a diester of the said hydroxylated aromatic or aliphatic dicarboxylic acid
and on a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol 1,2,4-butanetriol and 1,2,3-butanetriol, in a quantity corresponding to a ratio of number of OH functional groups of the polyol monomer (P)/number of COOH functional groups or functional group equivalents of the diacidic monomers (A)+(SA)+(HA) of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3 the said sulphonated polyesters exhibiting 
a number molecular mass lower than 20 000,
a sulphur weight content of the order of 0.5 to 10%, preferably of the order of 1.2 to 8%
and a hydroxyl functional group content, expressed an OH equivalent/kg of polymer, higher than 0.2.
Examples of monomers (A), (SA), (HA) and (P) have already been mentioned above; the operating conditions for preparation of the said sulphonated polyesters are those or equivalent to those also described above.
The detergent compositions for washing textile articles, especially based on polyester fibres, which are particularly advantageous in respect of their ecotoxicological properties, are those containing:
of the order of 0.01 to 10% by weight, preferably of the order of 0.1 to 5% by weight, very particularly of the order of 0.2 to 3% by weight of a water-dispersible or water-soluble sulphonated polyester antisoiling agent described above
and of the order of 3 to 40% by weight, preferably of the order of 5 to 35% by weight, of at least one anionic surface-active agent chosen from the sulphates of C5-C24 saturated aliphatic alcohols optionally condensed with approximately 0.5 to 30 moles of ethylene oxide,
not more than 5% by weight of the said detergent composition being capable of consisting of another type of anionic surface-active agent with less advantageous ecotoxicological properties, such as C1-C18 alkylbenzenesulphonates.
Among the sulphates of optionally ethoxylated alcohols which may be used there may be mentioned the sulphates of unethoxylated C14-C15 (preferably C10-C15) alcohols, the sulphates of C8-C13 (preferably C10-C13) fatty alcohols condensed with approximately 1 to 30 (preferably 1 to 10) moles of ethylene oxide, and the sulphates of C14-C20 (preferably C14-C18) fatty alcohols condensed with approximately 4 to 30 moles (preferably 4 to 10 moles) of ethylene oxide.
Other additives of the type of those described below may be present in the detergent compositions besides the said sulphonated polyesters of the invention.
SURFACE-ACTIVE AGENTS, in quantities corresponding to approximately 3-40% by weight relative to the detergent composition, surface-active agents such as
Anionic Surface-active Agents
alkyl ester sulphonates of formula Rxe2x80x94CH(SO3M)xe2x80x94COORxe2x80x2, where R denotes a C8-C20, preferably C10-C15 alkyl radical, Rxe2x80x2 a C1-C6, preferably C10-C3 alkyl radical and M an alkali metal (sodium, potassium, lithium) cation, substituted or unsubstituted amonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium etc.) or one derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine etc.). Very particularly, the methyl ester sulphonates in which the radical R in C14-C16 may be mentioned;
alkyl sulphates of formula ROSO3M, where R denotes a C5-C24, preferably C10-C15 alkyl or hydroxyalkyl radical, M denotes a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives containing on average from 0.5 to 30, preferably from 0.5 to 10 EO and/or PO unite;
alkylamide sulphates of formula RCONHRxe2x80x2OSO3M, where R denotes a C2-C22, preferably C6-C20 alkyl radical, Rxe2x80x2 a C2-C3 alkyl radical, M denoting a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives containing on average from 0.5 to 60 EO and/or PO units;
salts of C5-C24 preferably C14-C20, saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulphonates, primary or secondary C8-C22 alkyl sulphonates, alkylglycerol sulphonates, the sulphonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulphonates N-acyl-N-alkyltaurates, alkyl phosphates, isethionates, alkylsuccinamates, alkylsulphosuccinates, sulphosuccinate monoesters or diesters, N-acylsarcosinates, alkylglycoside sulphates and polyethoxycarboxylates the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium etc.) or one derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine etc.);
Nonionic Surface-active Agents
polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units; the examples which may be mentioned are Tritons X-45, X-114, X-100 or X-102, marketed by Rohm and Haas Co.;
glucosamide, glucamide, glycerolamide;
polyoxyalkylenated C9-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene (oxyethylene, oxypropylene) units; examples which may be mentioned are Tergitol 15-S-9, Tergitol 24-L-6 NMW marketed by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4 marketed by Shell Chemical Co. and Kyro EOB marketed by the Procter and Gamble Co.;
the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with propylene glycol, such as the Pluronics marketed by BASF;
the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such as the Tetronics marketed by BASF;
amine oxides such an (C10-C13 alkyl)dimethylamine oxides and (C5-C22 alkoxy)ethyldihydroxyethylamine oxides;
the alkylpolyglycosides described in U.S. Pat. No. 4,565,647;
C8-C20 fatty acid aides
ethoxylated fatty acids
ethoxylated fatty amides
ethoxylated amines
Catonic Surface-active Agent
alkyldimethylammonium halides.
Amphoteric and Zwitterionic Surface-active Agents
alkyldimetlylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulphobetaines, the products of condensation of fatty acids and of protein hydrolysates
alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.
ADJUVANTS IMPROVING THE PROPERTIES OF THE SURFACE-ACTIVE AGENTS (xe2x80x9cBUILDERxe2x80x9d AGENTS), in quantities corresponding to approximately 5-50%, preferably to approximately 5-30 by weight for the liquid detergent formulations or to approximately 10-80%, preferably 15-50% by weight for the powder detergent formulations, builder agents such an
Inorganic (xe2x80x9cBuilderxe2x80x9d) Adjuvants
alkali metal, ammonium or alkanolamine polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates)
tetraborates or borate precursors
silicates, in particular those which have an SiO2/Na2O ratio of the order of 1.6/1 to 3.2/1 and the lamellar silicates described in U.S. Pat. No. 4,664,839
alkali or alkaline-earth metal carbonates (bicarbonates, sesquicarbonates)
cogranulates of hydrated alkali metal silicates and of alkali metal (sodium or potassium) carbonates rich in silicon atoms in Q2 or Q3 form, described in EP-A-10 488 868
crystalline or amorphous alkali metal (sodium, potassium) or ammnonium aminosilicates such as zeolites A, P, X etc.; zeolite A of particle size of the order of 0.1-10 micrometers in preferred
Organic (xe2x80x9cBuilderxe2x80x9d) Adjuvnats
water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylenediphosphonate salts etc.)
water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as
polycarboxylate ethers (oxydisuccinic acid and its salts, tartrate monosuccinic acid and its salts, tartrate disuccinic acid and its salts)
hydroxypolycarboxylate ethers
citric acid and its salts, mellitic acid, succinic acid and their salts
salts of polyacetic acids (ethylienediaminetetraacetates, nitrilotriacetates, N-(2-hydroxyethyl)nitrilodiacetates)
C5-C20 alkyl)succinic acids and their salts (2-dodecenylsuccinates, laurysuccinates)
carboxylic polyacetal esters
polyaspartic acid, polyglutamic acid and their salts
polyimides derived from the polycondensation of aspartic acid and/or of glutamic acid
polycarboxymethylated derivatives of glutamic acid or of other amino acids;
BLEACHING AGENTS, in quantities of approximately 0.1-20%, preferably approximately 1-10% by weight, optionally in combination with BLEACHING ACTIVATORS, in quantities of approximately 0.1-60%, preferably of approximately 0.5-40% by weight, agents and activators such as
Bleaching Agents
perborates such as sodium perborate monohydrate or tetrahydrate
peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulphate preferably used in combination with a bleaching activator generating a carboxylic peroxyacid in situ in the washing medium; among theme activators there may be mentioned tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzene sulphonate, pentaacetylglucone, octaacetyllactose etc.
percarboxylic acids and their salts (called xe2x80x9cpercarbonatesxe2x80x9d) such as magnesium monoperoxyphthalate hexahydrate, magnesium meta-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedicic acid, the nonylamide of peroxyauccinic acid and decyldiperoxysuciinic acid.
Theme agents may be used in combination with at least one of the antisoiling or antiredeposition agents mentioned below.
Mention may also be made of nonoxygenated bleaching agents acting by photoactivation in the presence of oxygen, agents such as sulphonated aluminium and/or zinc phthalocyanines
other ANTISOILING AGENTS, in quantities of approximately 0.01-10%, preferably approximately 0.1-5% and very particularly of the order of 0.2-3% by weight, agents such as
cellulose derivatives such as cellulose hydroxyethers, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl
polyvinyl esters grafted onto polyalkylene backbones, such as polyvinyl acetates grafted onto polyoxyethylene backbones (EP-A-219 048)
polyvinyl alcohols
polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene terephthalate units, with an ethylene terephthalate and/or propylene terephthalate (number of units)/polyoxyethylene terephthalate (number of units) molar-ratio of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates exibiting polyoxyethylene units which have a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (U.S. Pat. No. 3,959,230, U.S. Pat. No. 3,893,929, U.S. Pat. No. 4,116,896, U.S. Pat. No. 4,702,857, and U.S. Pat. No. 4,770,666);
the sulphonated polyester oligomers obtained by sulphonation of an oligomer derived from ethoxylated allyl alcohol, from dimethyl terephthalate and from 1,2-propylene diol, containing from3 1 to 4 sulphonated groups (U.S. Pat. No. 4,968,451)
polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and ending in ethyl or methyl units (U.S. Pat. No. 4,711,730) or polyester oligomers ending in alkylpolyethoxy groups (U.S. Pat. No. 4,702,857) or sulphopolyethoxy (U.S. Pat. No. 4,721,580) or sulphoaroyl (U.S. Pat. No. 4,877,896) anionic groups
other ANTIREDEPOSITION AGENTS in quantities of approximately 0.01-10% by weight for a powder detergent composition, of approximately 0.01-5% by weight for a liquid detergent composition, agents such as
ethoxylated monoamines or polyamines, ethoxylated amine polymers (U.S. Pat. No. 4,597,898, EP-A-11 984)
carboxymethyl cellulose
sulphonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulphosuccinate and of diethylene glycol (FR-A-2 236 926)
polyvinylpyrrolidones
CHELATING AGENTS for iron and for magnesium, in quantities of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, agents such an
aminocarboxylates such as ethylienediaminetetraacetates, hydroxyethyl ethylenediaminetriacetates, nitrilotriacetates
aminophosphonates such as nitrilotris (methylenephosphonates)
polyfunctional aromatic compounds such as dihydroxydisulphobenzenes;
POLYMERIC DISPERSING AGENTS, in a quantity of the order of 0.1-7% by weight, to control the calcium and magnesium hardness, agents such as
the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100 000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid or methylenemalonic acid, and very particularly the polyacrylates of molecular mass of the order of 2 000 to 10 000 (U.S. Pat. No. 3,308,067) and copolymers of acrylic acid and of maleic anhydride of molecular mass of the order of 5 000 to 75 000 (EP-A-69 915)
polyethylene glycols of molecular mass of the order of 1000 to 50 000;
FLUORESCENCE AGENTS (BRIGHTENERS), in a quantity of approximately 0.05-1.2% by weight, agents such as stilbene derivatives, pyrazoline, coumarine, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes etc. (xe2x80x9cThe production and application of fluorescent brightening agentsxe2x80x9dxe2x80x94M. Zanradnik, published by John Wiley and Sons, New Yorkxe2x80x941982);
FOAM-SUPPRESSOR AGENTS, in quantities which may range up to 5% by weight, agents such an
C10-C24 monocarboxylic fatty acids or their alkali metal, ammonium or alkanolamine salts, fatty acid triglycerides
aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as the paraffins and waxes
N-alkylaminotriazines
monostearyl phosphates, monostearyl alcohol phosphates
polyorganosiloxane oils or resins optionally combined with silica particles;
SOFTENING AGENTS, in quantities of approximately 0.5-10% by weight, agents such as clays;
ENZYMES in a quantity which may range to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme/g of detergent composition, enzymes such as
proteases, amylases, lipases, cellulases, peroxydases (U.S. Pat. No. 3,553,139, U.S. Pat. No. 4,101,457, U.S. Pat. No. 4,507,219, U.S. Pat. No. 4,261,868):
OTHER ADDITIVES such as
alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerine)
buffer agents
perfumes
pigments.